Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/25—Component parts, details or accessories; Auxiliary operations
  • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
  • B29C48/465—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using rollers
  • B29C48/467—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using rollers using single rollers, e.g. provided with protrusions, closely surrounded by a housing with movement of the material in the axial direction
  • B29C48/468—Cavity transfer mixing devices, i.e. a roller and surrounding barrel both provided with cavities; Barrels and rollers therefor
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
  • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion

Definitions

• the subject matter of this invention concerns a process for the short-time treatment of plastic melt with a liquid treatment agent at a pressure and temperature at which the treatment agent is in the liquid state, with the mixture being subsequently expanded and subjected to degassing at a reduced pressure.
• the subject matter of this invention also concerns transparent thermoplastic materials which contain a poly(methacrylimide) plastic or transparent polymer mixtures produced therefrom with poly(methyl methacrylate).
• a treatment process of the type mentioned above is employed, for example, to convert poly(methyl methacrylate) into poly(methacrylimide) plastics.
• poly(methyl methacrylate) is melted in an extruder, and ammonia or a primary amine is incorporated into the melt using pressure.
• These treatment agents in combination with the polymerized units of methyl methacrylate, are converted into cyclic glutarimide units of the formula: ##STR1## in which R preferably stands for a hydrogen atom or a methyl group.
• methanol is cleaved off and subsequently withdrawn from the extruder by evaporation under reduced pressure in the degassing zone of the extruder.
• the degree of this reaction which is known as imidization, depends on the molar ratio between the ammonia or amine and the simultaneously present units of methyl methacrylate. With an excess of ammonia or amine, a considerable or complete imidization is obtained, while with substoichiometric quantities, a partial imidization is achieved. At the same time, units of methacrylic acid or methacrylic acid anhydride form.
• melts of thermoplastic materials are mixed under pressure with highly liquid treatment agent.
• a liquid blowing agent is incorporated into a plastic melt, the mixture is cooled and expanded in the thermoelastic state to form a foamed plastic.
• a special mixing device is used, which is connected to an extruder.
• the mixing device is equipped with a rotor which is supported in a stator in such a way that a gap is formed, through which the mixture consisting of a blowing agent and thermoplastic materials can pass while the rotor is turning.
• the outside surface of the rotor and the inside surface of the stator are fitted with cavities that are arranged so as to overlap one another during the rotation of the rotor, thus causing the mixture consisting of the blowing agent and the thermoplastic materials to be transferred from one cavity to the next while the mixture passes through the mixing device.
• the formation of more highly imidized quantities during the reaction of a poly(methyl methacrylate) melt with ammonia or an amine in the extruder is apparently due to the rapid reaction.
• the ammonia or amine which has been incorporated into the melt, reacts more rapidly with the methyl methacrylate units that are available in the immediate vicinity than it is being dispersed in the melt.
• this objective can be reached by dividing the plastic melt into defined subquantities, by bringing such individual subquantities into contact with the treatment agent and by combining them over a residence time of less than one second with portions of at least one other defined subquantity and by separating portions from the thus formed mixture and combining them with another defined subquantity and by repeating the steps of separating and combining the defined subquantities of the plastic melt several times at intervals of less than one second until an intimate mixture consisting of the plastic melt and the treatment agent is obtained.
• the treatment agent is rapidly dispersed in the melt, thus ensuring that the treatments lead to a homogeneous product.
• the mechanical dispersion of the melt does not reach the level of molecular dispersion, such as is achieved for a polymer solution according to European Patent EP-A 376,748. It is therefore surprising that the mechanical division and combination leads to a comparably successful result.
• the process claimed by this invention can be applied to many different treatment processes, it is of particular importance in those cases, in which the treatment agent as such or a secondary product, which is released during the treatment, is volatile and can thus be drawn off during the subsequent degasification. Even highly liquid treatment agents, the incorporation of which into a plastic melt can normally be achieved only with difficulty, can be used in the process according to this invention. Under the pressure and temperature conditions used, the treatment agent should be liquid or at least within the range of the supercritical state.
• the treatment agent may be reactive with respect to the plastic.
• An important practical example is the partial reaction of poly(methyl methacrylate) with ammonia or amines to form methyl methacrylate/methacrylimide copolymers.
• a case, in which it is undesirable for the treatment agent to be reactive with respect to the plastic, is the devolatilisation of the carrier agent, i.e., the removal of the residual monomers by means of water from poly(methyl methacrylate) or other polymers with carboxylic ester groups.
• the process of this invention is preferably carried out by subjecting the plastic melt in the extruder to pressure and by introducing the melt into a mixing device which is equipped with a stator and a rotor. Between the stator and the rotor, a narrow gap is located. The treatment agent is introduced into the mixing device under at least equal pressure. The inside surface of the stator and the outside surface of the rotor are fitted with cavities for holding defined subquantities of the plastic melt.
• the cavities of the rotor and stator overlap one another for a short period of time in such a way that under the prevailing pressure, portions of the subquantities of melt, which are mixed with the treatment agent, are separated from each cavity and are exchanged between the cavities of the rotor and stator, as a result of which the separated portions enter the cavities that are located further downstream.
• a portion of the subquantity in one cavity of the rotor enters a cavity of the stator which is located further downstream while at the other end of this cavity, an equally large portion of the melt is simultaneously transferred into a cavity of the rotor.
• the transfer of the melt stops whenever one overlapping phase is concluded and starts again in the direction of rotation, as soon as a new overlapping phase involving the next cavity starts.
• the flow of melt is divided into further branches.
• Hindmarch (information brochure of Rapra Technology Ltd., Shawbury, Shrewsbury, Shropshire SY4 4NR, UK, of Nov. 15, 1988). These mixers are used predominantly for mixing thermoplastic materials with one another or with rubber materials, but also with other additives, such as pigments, fillers, lubricants, stabilizers, or antistatic agents. In all cases, the mixing procedures used served to effectively incorporate permanent components into a mixture. What was not known, however, was that these mixers make it possible to incorporate treatment agents with low viscosity into a melt, which treatment agents or their reaction products are subsequently removed by devolatilisation.
• the residence time during which an individual subquantity of the mixture consisting of the melt and the treatment agent remains in a cavity of the mixer between two dividing and combining steps, is generally in the range of 0.001 second and 1.0 second, preferably in a range from 0.01 to 0.1 second.
• the cavities of the rotor have shifted with respect to those of the stator so that it is possible for a new overlapping phase to begin.
• the mixture exits from the cavities of one wall and enters the downstream cavities on the other wall, thereby displacing a portion of the mixture present in these latter-mentioned cavities and pushing it into the downstream cavities of the opposite wall.
• the cavities in the stator and the rotor are positioned in rows along a peripheral line.
• the mixture enters a row that is located further downstream until at the end of the mixture, the mixture exits from the last row of cavities.
• the residence time is defined as the interval between two overlapping phases, regardless of the quantity of the transferred portion of the subquantities in the cavities.
• the alternating cycle of dividing and combining is repeated until the mixture has passed entirely through the mixer. If the stator and rotor contain Y rows with N cavities each, the material flowing into the mixer will be divided N 2Y times before it finally exits the mixer (F. Hensen).
• the residence time between two successive dividing cycles results from the quotient of the residence time in the mixer and the number of dividing steps; as a rule, it is far less than 1/1000 second.
• the size of the subquantities is determined by the volume of the cavities. They should be small enough to ensure that the treatment agent is able to sufficiently penetrate every subquantity and to have the effect desired. Subquantities in the range of 0.001 to 100 mL are desirable; preferably of the range of 0.01 to 50 mL, more preferably in the range of 0.05 to 10 mL.
• the pressure at the inlet of the mixer is generated by the extruder screw that ends just in front of the inlet and ranges, for example, 100 to 500 bar, preferably from 50 to 400 bar, more preferably from 10 to 250 bar. It is useful to mechanically couple the rotor of the mixer to the extruder screw which then drives the rotor.
• the treatment agent is pressed at least the same pressure, preferably at a slightly higher pressure, through openings in one or several cavities of the first row of cavities.
• the pressure drop along the mixer up to the outlet of the mixer is generally 5 to 50 bar, thus making the mixture exit from the mixer at a pressure of 5 to 200 bar. It is recommended that this pressure be maintained as constant as possible during continuous operation. This can be achieved by introducing the mixture via a controlled pressure regulating valve into the degassing zone.
• the control variable used is the pressure prior to entry into the mixer; as this pressure rises, the pressure regulating valve opens wider and vice versa.
• the mixture is degassed after a residence time which can be freely chosen and which is determined by the flow rate from the time of exiting the mixer to the entry into the degassing zone. During this time, there is no longer a risk that the mixture is subjected to nonhomogeneous changes.
• the residence time can be set to be sufficiently long to ensure that the homogeneous reaction desired can take place or it can be set for such a short time that undesired changes are avoided.
• Devolatilisation can be suitably carried out in a conventional degassing extruder, in which the mixture is transported into a zone of reduced pressure.
• this degassing extruder can be connected directly to the mixer and can be driven by the same axis, it is preferable for the purpose of a more accurate pressure control in the mixer that the degassing extruder be kept separate from the mixer and that the mixture be introduced from the mixer via a line with the above-mentioned pressure regulating valve into the degassing extruder.
• a temperature in a range identical to that of the melt is maintained, which temperature as a rule corresponds approximately to that in the mixer.
• the pressure in the degassing zone depends on the vapor pressure of the component that is to be degassed. At times, it suffices to maintain a pressure in the degassing zone which is slightly lower than that in the mixer.
• degasification is carried out at atmospheric or subatmospheric pressure, optionally in several decremental pressure stages until the final pressure reached is in a range from 1,000 to 100 mbar, preferably from 600 to 50 mbar, more preferably from 400 to 10 mbar.
• the vapors from the degassing zone are drawn off using conventional methods.
• the pressure of the melt is once again increased, and the melt is subsequently discharged via a nozzle and cooled.
• thermoplastic materials can be treated according to the process described by this invention.
• Plastics to be preferred are plastics which can be processed at melt temperatures of 100° C. to 500°, preferably of 180° C. to 320° C. and which have a melt viscosity of 500 to 20,000 Pa.s, preferably of 1,000 to 15,000 Pa.s.
• Polymers suitable for the present application include, but are not limited to, the thermoplastic polymers produced by polymerization of esters of methacrylic acid with low molecular weight alcohols. Such esters include but are not limited to methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate.
• suitable polymers for the present application include esters of acrylic acid with low molecular weight alcohols such as methyl acrylate, ethyl acrylate, propyl acrylate and butyl acrylate.
• suitable polymers for the present invention include the copolymers of methacrylate esters with acrylate esters, styrene, ⁇ -alkyl substituted styrene, such as ⁇ -methyl styrene, ring substituted alkyl styrene, such as 2-methyl styrene, 3-methyl styrene, 4-methyl styrene, di- or tri-alkyl substituted styrenes, such as 2,3-dimethyl styrene, halide substituted styrene such as 2-chloro styrene, 2,5-difluoro styrene, maleic acid anhydride, itaconic acid anhydride and mixtures thereof of such
• the increased homogeneity of the plastics treated by means of the method described by this invention does not only promote the internal compatibility of said plastics but also the miscibility of these plastics with other thermoplastic materials. This has an especially favorable effect during the partial imidation of poly(methyl methacrylate).
• methyl methacrylate/methacrylimide copolymers with a degree of imidation of 0.5 to 15% are obtained.
• Primary aliphatic amines with 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms and especially methylamine, are to be preferred. These are preferably used in the form of a 1 wt.
• thermoplastic materials which can be prepared according to this invention, have the following copolymer composition:
• Glutarimide units are defined as the dimethacrylimide groups, the formulas of which were given in the introduction and in which R stands for hydrogen atoms or low alkyl groups, especially one with 1 to 6 C atoms, preferably with 1 to 4 C atoms, more preferably methyl.
• the Vicat softening temperatures of the reaction products range from 100° C. to 150° C., preferably from 110° C. to 130° C. These products are marked by a high transparency which is measured on the basis of a particularly low turbidity value (haze according to ASTM D 1003) and which, surprisingly, is not lost even when the products are mixed with poly(methyl methacrylate) molding materials, such as polymer mixtures consisting of
• Such mixtures have Vicat softening temperatures in a range from 110° C. to 130° C. They can be suitably used in many areas of application, in which so far predominantly poly(methyl methacrylate) had been used, e.g., for light covers of automotive vehicles, but they have the additional advantage of being able to withstand higher heat loads while having an unchanged excellent weathering resistance.
• the materials of the present invention are also suitable for applications demanding high heat resistance combined with transparency, in which applications more expensive materials have been used in the past, such as hisphenol-A-polycarbonate and tetramethyl bisphenol-A-polycarbonate.
• the treatment device used is a device which consists of a reaction extruder, a pressure regulating valve that is located downstream thereof, and a degassing extruder with two degassing openings, which are connected to a 40 mbar vacuum line.
• a poly(methyl methacrylate) (PMMA) molding material (with 1 wt % of methyl acrylate units) are added to this device.
• 10 kg of a poly(methyl methacrylate) (PMMA) molding material (with 1 wt % of methyl acrylate units) are added to this device.
• 10 g of methylamine per hour are added under pressure at a temperature of 250° C and a pressure of 100 bar into the melt by means of a metering pump.
• the reaction mixture is allowed to expand through the pressure regulating valve into the degassing extruder.
• the molding material that is discharged at the discharge end of the degassing extruder is glass-clear.
• Example 1 The process described in Example 1 is repeated with a molding material consisting of pure poly(methyl methacrylate). Per kg of molding material, 5 g of a 40% aqueous methylamine solution are added.
• the molding material obtained contains 5.3 wt % of dimethacryl-N-methylimide units and has a Vicat softening point of 125° C.
• a residual monomer content of 100 ppm of MMA was determined.
• the molding material produced according to Example 2 is compounded in a single-screw extruder in a ratio of 50:50 parts by weight with a PMMAmolding material (with 1 wt % of methyl acrylate units). From the mixture, specimens with a diameter of 50 mm and a thickness of 4 mm are injection-molded to determine the optical properties. The transmission measured was 91.6%, the turbidity (haze, 23° C.) was 0.9%. The (Differential Scanning Calorimetry) and resulted in one region at 125° C. only.
• the molding material produced as described in Example 1 was compounded with a sufficient quantity of an agent for modifying the impact strength (emulsion polymer with a butyl acrylate core and a PMMA shell), manufactured according to German Patent DE 3,842,796, to ensure that a molding material with 14 wt % of polymerized butyl acrylate was obtained. From this molding material, specimens were injection-molded for the purpose of determining the impact strength, the dimensional stability under heat, and the optical properties.
• an agent for modifying the impact strength emulsion polymer with a butyl acrylate core and a PMMA shell
• VST/B50 Vicat softening temperature
• Example 1 In the reaction extruder described in Example 1, the stator of the mixing unit was replaced with a smooth hollow cylinder section without cavities and the rotor was replaced with a screw unit with a diameter of 45 mm; both components had a length of 5D. The screw unit was double-threaded, and the screw flights were designed in such a way that per 1 D of pitch, 8 bars were obtained. Using the device which was modified as described above, the process according to Example 1 was repeated under the same conditions. Methylamine was introduced into the metering region of the reaction extruder.
• Example 2 After reacting and degassing the substance as described in Example 1, a molding material was obtained, from which the specimen was injection-molded. In this specimen, a turbidity (haze, 23° C.) of 18% was determined.

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• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Processes Of Treating Macromolecular Substances (AREA)
• Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

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• 1994
  • 1994-01-29 DE DE4402666A patent/DE4402666A1/de not_active Withdrawn
• 1995
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